Aromatic hydroxy sulfides



"UNITED jijfowlce Albertj Algron, Ohio, assignor to The Firestone Tire' & Rubbz "-'Coii1pahy,""'Akron,

, 'ijohimia corporation ofOhio 'jNoDraw' 'g; Application January 26,1946, "Serial No. 6 13,8225

3 Claims. (01. 260--609) 1 2 This invention relates to the dicresol sulfides di(3-methyl-4-undecyl-6-ethylphenol) monosulprepared from dialkylated meta-cresols, having ficle a total of at least 6 carbon atoms and no more di(3-methy1-4,6-didecylphenol) monosulfide than a t ato s in the two al yl b di(3-methyl4-buty1-6-ocylphenol) monosulfide uents. Preferably, each alkyl substituent con- 5 di(3-methyl-4-tertiary-butyl-6-octylphenol) ditains at least 3 carbon atoms and may contain sulfide Ztfiiiefi litie 3efi tttnt ittmffii Z5222??? e a m from which. the sulfides agents for reclaiming vulcanizates, such as cured of l fi ig; zgz g gf gg g 32 rubber-like copolymers of butadiene and styrene f i 8 Su r p tion 5 which are not softened by the reclaiming agents P s y t ch s commonly used in vulcanizing cured natural rubchlonde m solutlqn m an ner so ven her (my Copendin ap lie ation S erial N 0 753 361) carbon tetrachloride or ethylene dichloride, etc.

. g p when sulfur monochloride, S2C12, is used, the

The dicresol sulfides of this invention also have duct robabl contains in addition to the value as stabilizers for synthetic rubber latices, 1310 g i 1k 1 t d res 150 6 (sub such as latices of rubber-like copolymers of (1) momsu e of e y a e c o m butadiene and styrene and (2) butadiene and acrylonitrile. They are also stabilizers for the coagulated copolymers.

The di(dialkyl cresol) sulfides of this invention 20 include the monosulfides, the disulfides, and the polysulfides. The following formula represents the preparation of the dialkylated cresol monosulfide which is preferred for reclaiming, the reaction is preferably carried out with sulfur dichloride, SClz, and advantageously at room temperature. The following examples illustrate the invention: the various dicresol sulfides of this invention. EXAMPLE 1 H CH3 OH SI'ILFUR DIcHLoRnm METHOD 5. Di 4,6-di-tertiary-butyl-3-methylphenol) sulfide R2 R1 R1 Forty grams of 4,6-d1-tertiary-butyl-3-methylphenol were dissolved in 400 ml. of carbon tetra- 1n Whlch R1 and R2 are alkyl groups, the Su chloride. To this 9.4 grams of sulfur dichloride of whose carbon atoms equals 6 to about 20, and were added over a lyrhour period at room R14 and R2 each preferably contam 3 to about 10 perature. After the addition had been completed,

carbon atoms and a7 is 1 to The term the reaction mixture was allowed to stand several fides as used in this text, therefore, includes hours, and than it was refluxed for 3 h Th monosulfide, disulfide and polysllfidescrude dicresol sulfide was obtained by evaporat- The preferred reclaiming agents are di(3'meth 0 ing the solvent. It was a reddish-brown resin 31'4'6di-terfiMY-butylphenol) sulfides and which was solid at room temperature and liquid (3 methyl 4,6 tertiary amylphenol) sulfides. at Q Other dialkyl cresol sulfides of the invention EXAMPLE 2 include:

i(3-m th 1-4 6-di-tertia -but 1 h n 1) d1 1- 40 SULFUR MONOCHLORIDE METHOD d fide y ry yp e 0 Dz'(4,6-di-tertiary-butyl-3-methylphenol) sulfide di(3-methyl-4,6-ditertiary 'amylphenol) disul- Two hundred and twenty grams of 4,6-di-terfide tiary-butyl-m-cresol were dissolved in 330 grams di(3-methy1-4,6-diheptylphenol) monosulfide or" carbon tetrachloride over a 45-minute period. di(3-methyl-4,6-diheptylphenol) disulfide A solution of 67.5 grams of sulfur monochloride di(3-methyl-4,6-di-tertiary-butylphenol) polyin grams of carbon tetrachloride was added. sulfide The reaction mixture was refluxed for 2 hours,

di(3-methyl-4,6-di-isopropy1 heno1) monosulfide and then dry air was blown through the solution di(3-methyl-4,6-di-isopropylphenol) disulfide 50 to remove any hydrogen chloride. The dicresol di(3-methyl-4,6-di-isopropylphenol) polysulfide vsulfide was obtained by evaporating the solvent. d1(3-methyl-4-tertiary-butyl-6-isopropylphenol) The yield of crude product was quantitative. It monosulfide was a reddish-brown resin which was solid at di(3-methyl-4-ethyl-fi-undecylphenob monosulroom temperature and liquid at 100 C. On coolfide (5 ing from 100 0., solidification started at C.

fide and tertasulfide as well as free sulfur. For

A portion 01 the product was recrystallized 3 times from benzene. It was then found to have a melting point of 296-208 C., uncorrected. Analysis of this purified compound for sulfur by the micro Carius method gave the following results:

, Sulfur: calculated for C30H46O2S, 6.82 per cent; found, 6.38 per cent.

The other di(4,6-dialky1-meta-cresol) sulfides of this invention may be similarly prepared. Other methods of preparation may be employed.

What I claim is:

1. Di(4,6-di-tertiary-buty1 meta cresol) sull- 2. Di(4,6-di-tertiary-butyl-meta-cresol) mono-' REFERENCES CITED The following references are of record in the file of thispatent:

UNITED STATES PATENTS Number -Name Date 1,912,588 Moses et al. June 6, 1933 2,256,441 Rieff Sept. 16, 1941 2,256,443 Rieff Sept. 16, 1941 2,270,183 Cook Jan. 13, 1942 2,364,338 Beaver Dec. 5, 1944 2,379,755 Sib1ey- Mar. 6, 1945 2,381,854 Rieff Aug. '7, 1945 2,402,448 Richards June 18, 1946 2,409,687 7 Rogers et a1 Oct. 22, 1946 2,449,026" Gilder Sept. 7, 1948 

1. DI(4,6-DI-TERTIARY-BUTYL - META - CRESOL) SULFIDES. 